Carbon containing silicon oxide film having high ashing tolerance and adhesion

ABSTRACT

An insulating film used for an interlayer insulating film of a semiconductor device and having a low dielectric constant. The insulating film comprises a carbon containing silicon oxide (SiOCH) film which has Si—CH2 bond therein. The proportion of Si—CH2 bond (1360 cm−1) to Si—CH3 bond (1270 cm−1) in the insulating film is preferably in a range from 0.03 to 0.05 measured as a peak height ratio of FTIR spectrum. The insulating film according to the present invention has higher ashing tolerance and improved adhesion to SiO2 film, when compared with the conventional SiOCH film which only has CH3 group.

FIELD OF THE INVENTION

The present invention relates generally to an insulating film having alow dielectric constant, and more particularly to an insulating filmhaving a low dielectric constant which is used, for example, as aninterlayer insulating film of a semiconductor device.

BACKGROUND OF THE INVENTION

Recently, according to an increase in demand for higher integrationdegree of a semiconductor device, a multi-layer wiring technology hasbecome of much note. In the multi-layer wiring structure, a bottleneckagainst high speed operation of elements is capacitance between wires.In order to decrease the capacitance between wires, it is necessary toreduce the dielectric constant (or relative dielectric constant) of aninterlayer insulating film.

Conventionally, a silicon dioxide (SiO2) film is generally used.Recently, however, other insulating film materials having lowerdielectric constant are energetically developed. The conventionalsilicon dioxide film is formed by adding oxygen O2 or nitrous oxide N2Oas oxidizing agent to material gas such as SiH4, Si(OC2H5)4 and thelike, and by using a plasma enhanced CVD method and the like. Thedielectric constant of silicon dioxide obtained in this way isapproximately 4.0. On the other hand, it is reported that a carboncontaining silicon oxide (SiOCH) film, which is formed by using methylsilane based precursor (for example, trimethyl silane or tetramethylsilane) as material gas and which is formed by using a plasma enhancedCVD method, has the dielectric constant of 3 or lower. In the SiOCHfilm, CH3 group as an end group is introduced into —O—Si—O— network,thereby reducing the density to decrease the dielectric constantthereof. For example, see page 3, column 2 through page 4, column 4 ofthe specification of U.S. Pat. No. 6,159,871, and page 11, column 4through page 16, column 14 of the specification of U.S. Pat. No.6,054,379.

However, the CH3 groups contained in the SiOCH film are often destructedin the O2 ashing process when trenches and vias are formed in the film.Therefore, the SiOCH film is susceptible to deterioration of filmquality such as film contraction, moisture absorption and the like. Thisis because, the CH3 group is located in the end portion of the —O—Si—O—network, and easily reacts with O ions and radicals in the ashingatmosphere.

At present, in developing next generation devices, an effort isenergetically performed to further reduce the dielectric constant bymaking the SiOCH film porous. However, when the SiOCH film becomesporous, the above-mentioned ashing damage becomes prominent. Also, inthe via-first method which is most typical among the dual-damasceneprocesses for forming wiring structure, side walls of the through holes(vias) formed in the process of the method are exposed to the ashingprocesses twice when the vias are formed and when the trenches areformed. When the side walls of the vias are deteriorated due to theashing damage and moisture absorption becomes large, deterioration ofyield of vias becomes large.

Further, when the SiOCH film is patterned, an SiO2 film (CAP-SiO2 film)is formed on the SiOCH film as a mask for patterning. However, adhesionof the SiOCH film with the CAP-SiO2 film is lower than that of theconventional film such as an SiO2 film, an SiON film, an SiN film, anHSQ film and the like. This is because, the CH3 groups contained in thefilm is hydrophobic, and affinity thereof with the SiO2 film isrelatively low.

SUMMARY OF THE INVENTION

Therefore, it is an object of the present invention to provide aninsulating film which can be used as an interlayer insulating film of asemiconductor device and in which ashing tolerance of the insulatingfilm can be improved without causing a rise in dielectric constant ofthe insulating film.

It is another object of the present invention to provide an insulatingfilm which can be used as an interlayer insulating film of asemiconductor device and which has improved adhesion with an SiO2 film.

It is still another object of the present invention to provide asemiconductor device having an interlayer insulating film in whichashing tolerance of the interlayer insulating film can be improvedwithout causing a rise in dielectric constant of the insulating film.

It is still another object of the present invention to provide asemiconductor device having an interlayer insulating film in which theinterlayer insulating film has improved adhesion with an SiO2 film.

It is still another object of the present invention to obviate thedisadvantages of the conventional insulating film and the semiconductordevice using the conventional insulating film.

According to an aspect of the present invention, there is provided aninsulating film comprising a carbon containing silicon oxide (SiOCH)film which has Si—CH2 bond in the carbon containing silicon oxide film.

According to another aspect of the present invention, there is provideda semiconductor device having an interlayer insulating film formed on orover a semiconductor substrate and a metal wiring conductor which isformed by filling a wiring trench formed in the interlayer insulatingfilm with Cu containing metal via a barrier metal, wherein theinterlayer insulating film includes the insulating film comprising acarbon containing silicon oxide (SiOCH) film which has Si—CH2 bond inthe carbon containing silicon oxide film.

According to still another aspect of the present invention, there isprovided a semiconductor device having an interlayer insulating filmformed on or over a semiconductor substrate, an opening which is formedin the interlayer insulating film and which reaches a lower layer metalwiring conductor, and a metal plug which is formed by filling theopening with Cu containing metal via a barrier metal, wherein theinterlayer insulating film includes the insulating film comprising acarbon containing silicon oxide (SiOCH) film which has Si—CH2 bond inthe carbon containing silicon oxide film.

According to still another aspect of the present invention, there isprovided a semiconductor device having an interlayer insulating filmformed on or over a semiconductor substrate, a wiring trench formed inthe interlayer insulating film, an opening which is formed in theinterlayer insulating film and which reaches a lower layer metal wiringconductor from the bottom portion of the wiring trench, and a metalwiring conductor and metal plug which are formed by filling the wiringtrench and the opening with Cu containing metal via a barrier metal,wherein the interlayer insulating film includes the insulating filmcomprising a carbon containing silicon oxide (SiOCH) film which hasSi—CH2 bond in the carbon containing silicon oxide film.

In the above, it is preferable that the proportion of Si—CH2 bond (1360cm−1) to Si—CH3 bond (1270 cm−1) in the insulating film is in a rangefrom 0.03 to 0.05 measured as a peak height ratio of FTIR spectrum.

It is also preferable that the relative dielectric constant of theinsulating film is equal to or lower than 3.1.

It is further preferable that the carbon containing silicon oxide(SiOCH) film is formed by using plasma enhanced CVD process.

It is advantageous that the carbon containing silicon oxide (SiOCH) filmcomprises methylsilsesquioxane.

It is also advantageous that, as a portion of the interlayer insulatingfilm, an SiO2 film is formed on the upper layer portion of theinsulating film.

It is further advantageous that, as a portion of the interlayerinsulating film, an insulating film for preventing metal diffusion isformed on the lower layer portion of the insulating film.

It is preferable that the Cu containing metal contains, in addition toCu, at least one of Si, Al, Ag, W, Mg, Be, Zn, Pd, Cd, Au, Hg, Pt, Zr,Ti, Sn, Ni and Fe.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, and advantages, of the present invention willbe more clearly understood from the following detailed description takenin conjunction with the accompanying drawings, in which like referencenumerals designate identical or corresponding parts throughout thefigures, and in which:

FIG. 1 is a schematic view illustrating a plasma enhanced CVD systemused for forming an insulating film according to the present invention;

FIG. 2A is a graph showing the RF power dependence of FT-IRcharacteristics of insulating films according to the present invention,and especially showing peak curves of Si—CH2 in FT-IR spectra of SiOCHfilms formed in various RF power conditions;

FIG. 2B is a graph showing the RF power dependence of FT-IRcharacteristics of insulating films according to the present invention,and especially showing peak curves of Si—CH3 in FT-IR spectra of SiOCHfilms formed in various RF power conditions;

FIG. 2C is a table showing ratios of Si—CH2 to Si—CH3 of SiOCH filmsformed in various RF power conditions;

FIG. 3 is a graph showing relationships between Si—CH2/Si—CH3 bond ratioand relative dielectric constant, and between Si—CH2/Si—CH3 bond ratioand a rise in dielectric constant caused by ashing, in an insulatingfilm according to the present invention;

FIG. 4 is a graph showing a relationship between Si—CH2/Si—CH3 bondratio and adhesion, in an insulating film according to the presentinvention;

FIG. 5 is an illustration showing relationships between parametersconcerning various film forming conditions and Si—CH2/Si—CH3 bond ratio;

FIG. 6 is a cross sectional view showing a semiconductor deviceaccording to an embodiment of the present invention;

FIGS. 7A–7D are cross sectional views illustrating in order a process offorming the semiconductor device shown in FIG. 6;

FIG. 8 is a graph showing a relationship between Si—CH2/Si—CH3 bondratio and defects after a CMP process of an insulating film in theembodiment of the present invention shown in FIG. 6;

FIGS. 9A–9D are cross sectional views illustrating in order a process offorming a semiconductor device according to another embodiment of thepresent invention; and

FIG. 10 is a graph showing a relationship between Si—CH2/Si—CH3 bondratio and yield of an insulating film in the embodiment of the presentinvention shown in FIGS. 9A–9D.

DESCRIPTION OF A PREFERRED EMBODIMENT

With reference to the drawings, embodiments of the present inventionwill now be described.

Embodiment 1

In this embodiment, an explanation will be made on a method of formingan insulating film according to the present invention, that is, an SiOCHfilm having Si—CH2 bond in the film, on a semiconductor substrate. FIG.1 illustrates a schematic structure of a parallel plate electrode typeplasma enhanced CVD apparatus which can be used for forming the SiOCHfilm according to the present invention.

The apparatus shown in FIG. 1 comprises a processing chamber 17 withinwhich film forming process is performed on a semiconductor substrate 11,and a susceptor 12 which is disposed in the processing chamber 17 andwhich functions as a lower plate electrode. The susceptor 12 has aheater for heating a semiconductor substrate 11 placed on the susceptor12 and for keeping the temperature of the semiconductor substrate 11constant. The apparatus shown in FIG. 1 also comprises a transportingmeans (not shown in the drawing) for carrying the semiconductorsubstrate 11 into the processing chamber 17 and for carrying thesemiconductor substrate 11 out of the processing chamber 17. Theapparatus shown in FIG. 1 further comprises an exhaust means 13 whichkeeps the pressure in the processing chamber 17 constant, a gas supplyportion 14 which supplies a plurality of kinds of reaction gases intothe processing chamber 17, and a high frequency signal generator 15.

Within the processing chamber 17, there are provided an upper plateelectrode 16 and the susceptor 12 as a lower plate electrode in opposeddispositions. The upper plate electrode 16 is electrically coupled withthe high frequency signal generator 15 mentioned above. Also, thesusceptor 12 has the heater mentioned above which is built therein. Thehigh frequency signal generator 15 generates and supplies a highfrequency power (RF power) signal, which has a predetermined frequencyand a predetermined high frequency power, between the upper plateelectrode 16 and the susceptor 12 as the lower plate electrode.

When the SiOCH film is formed by using the plasma enahnced CVD apparatuswhich has the above-mentioned structure, the semiconductor substrate 11placed on the susceptor 12 is heated to a desired temperature by theheater built in the susceptor 12. Also, predetermined kinds of reactiongases are supplied into the processing chamber 17 at predetermined flowrates, thereby a desired gas atmosphere and a desired processingpressure are realized within the processing chamber 17. A high frequencyRF power signal having a desired frequency is applied between the upperplate electrode 16 and the susceptor 12, and plasma of reaction gases isproduced within the processing chamber 17. Thereby, the SiOCH film isformed on the semiconductor substrate 11.

Next, a detailed explanation will be made on a method of forming theSiOCH film by using the above-mentioned plasma enahnced CVD apparatus.In this embodiment, trimethyl silane and oxygen were used as sourcegases to form the SiOCH film. In a typical film forming condition, afilm forming temperature is 350° C., and source gases comprise trimethylsilane at a flow rate of 1100 sccm and oxygen (O2) at a flow rate of 450sccm. Also, an RF power is 700 W, and a pressure is 4.5 Torr.

Also, the inventors formed SiOCH films having various filmcharacteristics, by changing these film forming conditions, i.e., RFpower, gas flow rate, temperature and pressure, and measured the filmcharacteristics. As a result thereof, the inventors found that there areclose relationships between the proportion of Si—CH2 bond (1360 cm−1) toSi—CH3 bond (1270 cm−1) in each film in Fourier Transform InfraredSpectroscopy (FTIR) spectrum and film characteristics. That is, in afilm which has Si—CH2 bond, as the Si—CH2 bond/Si—CH3 bond ratio becomeshigher, ashing tolerance and adhesion become improved, and alsodielectric constant becomes larger. On the other hand, as the Si—CH2bond/Si—CH3 bond ratio becomes lower, a change in each of theseparameters shows an opposite tendency.

FIGS. 2A through 2C show peak curves of Si—CH2 in FTIR spectra, peakcurves of Si—CH3 in FTIR spectra, and ratios of Si—CH2 to Si—CH3calculated from these peak curves, respectively, concerning SiOCH filmsformed in various conditions in which RF powers are changed from 560 Wthrough 630 W, 700 W, 770 W and 840 W.

FIG. 2A shows peaks of Si—CH2 bond having a wave number of 1360 cm−1 inFTIR spectra. From FIG. 2A, it can be seen that, as the RF power becomeslarge, Si—CH2 bond increases.

FIG. 2B shows peaks of SiCH3 bond having a wave number of 1270 cm−1 inFTIR spectra. From FIG. 2B, it can be seen that, as the RF power becomeslarge, Si—CH3 bond decreases.

FIG. 2C is a table showing a result of ratios of Si—CH2 to Si—CH3calculated from these peak curves. From FIG. 2C, it can be seen that, asthe RF power increases, the ratios of Si—CH2 bond to Si—CH3 bondincrease.

With respect to the samples of SiOCH films obtained in this way andhaving the ratios of Si—CH2 bond to Si—CH3 bond shown in FIG. 2C, ashingtolerance and adhesion to the SiO2 film (CAP-SiO2 film) which is formedas the upper layer on the SiOCH film were examined.

With respect to the ashing tolerance, a parallel plate type O2 ashingapparatus was used, and ashing process was performed in the followingconditions. That is, flow rate of ashing gas, O2, was 500 sccm, RF powerwas 1000 W, process time was 60 seconds, and process temperature was100° C. FIG. 3 shows: relative dielectric constant of SiOCH film beforethe ashing process in ordinate of left side; and increase in relativedielectric constant of SiOCH film after the ashing process in ordinateof right side; with respect to the ratios of Si—CH2 to Si—CH3 shown bythe abscissa. From FIG. 3, it can be seen that, as Si—CH2 bondincreases, ashing tolerance is improved. On the other hand, as theSi—CH3 group decreases, the relative dielectric constant increases. Itcan be seen that, in a range of Si—CH2/Si—CH3 ratio from 0.03 to 0.05,relative dielectric constant is 3 or lower and increase in the relativedielectric constant caused by ashing becomes 0.1 or lower. That is, inthis range, it is possible to keep the relative dielectric constant ofSiOCH film equal to or lower than 3.1, even after performing the ashingprocess.

FIG. 4 shows a relationship between an adhesion of a CAP-SiO2 film andan Si—CH2/Si—CH3 ratio, measured by using a four point bending method.From FIG. 4, it can be seen that, when the Si—CH2/Si—CH3 ratio becomeshigh, the adhesion becomes improved. This is because, when theSi—CH2/Si—CH3 ratio becomes high, CH3 groups which are hydrophobicgroups decrease, and Si—CH2 bonds hide in —Si—O— network, so thataffinity for SiO2 film increases. Therefore, from the point of view ofadhesion, it is preferable that the Si—CH2 bond/Si—CH3 bond ratio ishigh. However, when the Si—CH2 bond/Si—CH3 bond ratio becomes high,dielectric constant also increases. Therefore, it is preferable that theSi—CH2 bond/Si—CH3 bond ratio is in a range from 0.03 to 0.05.

In the above, an explanation was made on an example in which RF powerwas changed to change Si—CH2 bond/Si—CH3 bond ratio. FIG. 5 showsrelationships between various parameters in forming the film and Si—CH2bond/Si—CH3 bond ratio. From FIG. 5, it can be seen that, when O2 flowrate is relatively low, when a pressure is relatively low and when atemperature is relatively high, the Si—CH2 bond/Si—CH3 bond ratiobecomes high. Therefore, by optimizing these parameters, it is possibleto form a SiOCH film having the Si—CH2 bond/Si—CH3 bond ratio of0.03–0.05.

By using the method mentioned above, it is possible to form aninsulating film according to the present invention, that is, an SiOCHfilm having Si—CH2 bond within the film. In this case, it is preferablethat the Si—CH2 bond/Si—CH3 bond ratio is in a range between 0.03 and0.05, and, by using the ratio in this range, it is possible to keep therelative dielectric constant of the SiOCH film equal to or lower than3.1 even after performing ashing.

Also, in the above, an explanation was made on a method of forming theSiOCH film by using a plasma enhanced CVD apparatus. However, by usingmethylsilsesquioxane (MSQ) formed by coating and by controlling basematerial, it is also possible to form an SiOCH film which has Si—CH2bond within the film, in which the Si—CH2 bond/Si—CH3 bond ratio is in arange between 0.03 and 0.05, and in which the relative dielectricconstant of the SiOCH film can be kept equal to or lower than 3.1 evenafter ashing.

Embodiment 2

An explanation will now be made on a second embodiment of the presentinvention. In the second embodiment, an SiOCH film according to thepresent invention is applied to a single damascene wiring structure.

FIG. 6 is a cross sectional view illustrating a semiconductor deviceaccording to the second embodiment of the present invention. In FIG. 6,reference numeral 81 designates a ground insulating film formed on asemiconductor substrate (not shown in the drawing) on whichsemiconductor elements such as transistors, capacitors and the like (notshown in the drawing) are formed. On the ground insulating film 81, afirst interlayer insulating film is formed which comprises, from a lowerlayer to an upper layer, a first SiCNH film 82, a first SiOCH film 83,and a first SiO2 film (i.e., first CAP-SiO2 film) 84. The first SiCNHfilm 82 is formed as an anti metal diffusion insulating film forpreventing diffusion of metal such as Cu and the like, and has a filmthickness of 50 nm. The first SiOCH film 83 is a film which has a filmthickness of 250 nm, and which has Si—CH2 bond therein and Si—CH2bond/Si—CH3 bond ratio thereof is preferably 0.03–0.05. The first SiO2film 84 has a film thickness of 100 nm.

In a wiring trench formed in the first interlayer insulating film, afirst Cu wiring conductor 87 is formed via a first Ta/TaN film 86. Thefirst Ta/TaN film 86 is formed as a barrier metal layer and has a filmthickness of 30 nm. The first Cu wiring conductor 87 is a first metalwiring conductor which comprises Cu as Cu containing metal.

On the upper surface of the first SiO2 film 84 and the first Cu wiringconductor 87, a second interlayer insulating film is formed whichcomprises, from a lower layer to an upper layer, a second SiCNH film 88,a second SiOCH film 89, and a second SiO2 film (i.e., second CAP-SiO2film) 90. The second SiCNH film 88 is formed as an anti metal diffusioninsulating film for avoiding diffusion of metal, and has a filmthickness of 50 nm. The second SiOCH film 89 is a film which has a filmthickness of 250 nm, and which has Si—CH2 bond therein and Si—CH2bond/Si—CH3 bond ratio thereof is preferably 0.03–0.05. The second SiO2film 90 has a film thickness of 100 nm.

In the second interlayer insulating film, there is formed an opening(i.e., a via) which penetrates through the second interlayer insulatingfilm and which reaches the first Cu wiring conductor 87, that is, thelower layer metal wiring conductor. In the opening, there is formed a Cuplug 93 via a second Ta/TaN film 92. The second Ta/TaN film 92 is formedas a barrier metal layer and has a film thickness of 30 nm. The Cu plug93 is a metal plug which comprises Cu as Cu containing metal.

On the upper surface of the second SiO2 film 90 and the Cu plug 93, athird interlayer insulating film is formed which comprises, from a lowerlayer to an upper layer, a third SiCNH film 95, a third SiOCH film 96,and a third SiO2 film (i.e., third CAP-SiO2 film) 97. The third SiCNHfilm 95 is formed as an anti metal diffusion insulating film foravoiding diffusion of metal, and has a film thickness of 50 nm. Thethird SiOCH film 96 is a film which has a film thickness of 250 nm, andwhich has Si—CH2 bond therein and Si—CH2 bond/Si—CH3 bond ratio thereofis preferably 0.03–0.05. The third SiO2 film 97 has a film thickness of100 nm.

In the third interlayer insulating film, there is formed a wiring trenchwhich penetrates through the third interlayer insulating film and whichreaches the Cu plug 93 of the lower layer. In the wiring trench, thereis formed a second Cu wiring conductor 99 via a thrid Ta/TaN film 98.The third Ta/TaN film 98 is formed as a barrier metal layer and has afilm thickness of 30 nm. The second Cu wiring conductor 99 is a secondmetal wiring conductor which comprises Cu as Cu containing metal.

Next, an explanation will be made on a method of manufacturing a singledamascene wiring structure shown in FIG. 6 to which SiOCH filmsaccording to the present invention are applied. FIGS. 7A–7D are crosssectional views each illustrating, in order of process steps, aworkpiece of a semiconductor device according to the second embodimentobtained during a process of manufacturing thereof.

With reference to FIG. 7A, first, on a ground insulating film 81 formedon a semiconductor substrate (not shown in the drawing) on whichsemiconductor elements such as transistors, capacitors and the like (notshown in the drawing) are formed, a first SiCNH film 82 is formed byusing a plasma enhanced CVD method to a film thickness of 50 nm. Then,also by using a plasma enhanced CVD method, a first SiOCH film 83 isformed to a film thickness of 250 nm. The first SiOCH film 83 has Si—CH2bond therein and Si—CH2 bond/Si—CH3 bond ratio thereof is preferably0.03–0.05. Thereafter, the first SiO2 film (i.e., first CAP-SiO2 film)84 is formed by using a plasma enhanced CVD method to a film thicknessof 100 nm. In this process, process temperature is 200–450° C., N2O gasflow rate is 100–6000 sccm, SiH4 gas flow rate is 10–1000 sccm, processpressure is 1–20 Torr, and RF power is 50–500 W. It is also possible toform the first SiO2 film 84 in the same vacuum chamber as that used forforming the first SiOCH film 83, continuously after forming the firstSiOCH film 83. By the process steps mentioned above, the firstinterlayer insulating film comprising three layers is formed whichcomprises, from a lower layer to an upper layer, the first SiCNH film82, the first SiOCH film 83, and the first SiO2 film 84.

Next, by using a photolithography technology and a dry etchingtechnology, a wiring trench 85 is formed which penetrates through thefirst SiO2 film 84, the first SiOCH film 83 and the first SiCNH film 82,as clearly shown in FIG. 7A.

With reference to FIG. 7B, on an exposed inside wall of the wiringtrench 85 and on the upper surface of the first SiO2 film 84, a Ta/TaNfilm 86 is formed to a film thickness of 30 nm. On the Ta/TaN film 86, aCu layer is formed to a film thickness of 100 nm by using a sputteringmethod. The Cu layer is used as a cathode side ground layer for anelectrolytic plating method. Thereafter, the wiring trench 85 is filledwith Cu by using an electrolytic plating method. Further, a heattreatment is performed thereafter at a temperature of 100–400° C. forcrystallization. Then, the Cu layer and the Ta/TaN film 86 on the firstSiO2 insulating film 84 are removed by a CMP method. Thereby, the firstCu wiring conductor 87 is formed within the wiring trench 85, as clearlyshown in FIG. 7B.

With reference to FIG. 7C, a second interlayer insulating film is formedon the workpiece obtained by the process mentioned above. That is, byusing a procedure similar to that mentioned above, a second SiCNH film88 is formed to a film thickness of 50 nm. Then, by using a plasmaenhanced CVD method, a second SiOCH film 89 is formed to a filmthickness of 250 nm which has Si—CH2 bond therein and Si—CH2 bond/Si—CH3bond ratio thereof is preferably 0.03–0.05. Further, a second SiO2 film(a second CAP-SiO2 film) 90 is formed to a film thickness of 100 nm.

By using a photolithography technology and a dry etching technology,there is formed an opening (i.e., a via) 91 which penetrates through thesecond interlayer insulating film and which reaches the first Cu wiringconductor 87, as clearly shown in FIG. 7C.

With reference to FIG. 7D, on an inside wall of the opening 91 and onthe upper surface of the second SiO2 film 90, a second Ta/TaN film 92 isformed to a film thickness of 30 nm. On the second Ta/TaN film 92, a Culayer is formed to a film thickness of 100 nm by using a sputteringmethod. The Cu layer is used as a cathode side ground layer for anelectrolytic plating method. Thereafter, the opening 91 is filled withCu by using an electrolytic plating method. Further, a heat treatment isperformed at a temperature of 100–400° C. for crystallization. Then, theCu layer and the Ta/TaN film 92 on the second SiO2 insulating film 90are removed by a CMP method. Thereby, a Cu plug 93 is formed within theopening 91 as a metal plug, as clearly shown in FIG. 7D.

Thereafter, referring back again to FIG. 6, a third interlayerinsulating film is formed on the workpiece obtained as mentioned above.That is, by using a procedure similar to that mentioned above, a thirdSiCNH film 95 is formed to a film thickness of 50 nm. Then, by using aplasma enhanced CVD method, a third SiOCH film 96 is formed to a filmthickness of 250 nm which has Si—CH2 bond therein and Si—CH2 bond/Si—CH3bond ratio thereof is preferably 0.03–0.05. Further, a third SiO2 film(a third CAP-SiO2 film) 97 is formed to a film thickness of 100 nm.

By using a photolithography technology and a dry etching technology,there is formed a wiring trench which penetrates through the thirdinterlayer insulating film and which connects at a portion thereof tothe Cu plug 93 of lower layer. Next, in a manner similar to the methodmentioned above, on an inside wall of the wiring trench and on the uppersurface of the third SiO2 film 97, a third Ta/TaN film 98 is formed, andon the third Ta/TaN film 98, a Cu layer is formed. The Cu layer is usedas a cathode side ground layer for an electrolytic plating method.Thereafter, the wiring trench is filled with Cu by using an electrolyticplating method. Further, a heat treatment is performed at a temperatureof 100–400° C. for crystallization. Then, the Cu layer and the Ta/TaNfilm 98 on the third SiO2 insulating film 97 are removed by a CMPmethod. Thereby, a second Cu wiring conductor 99 is formed within thewiring trench. By the process mentioned above, the two layer wiringstructure having a single damascene structure was formed.

FIG. 8 shows a relationship between a number of defects of Cu portionafter performing a CMP process and a film composition, i.e.,Si—CH2/Si—CH3 ratio, of a SiOCH film which is used as an interlayerinsulating film, when the above-mentioned Cu wiring conductor is formed.From FIG. 8, it can be seen that, as the proportion of Si—CH2 bond toSi—CH3 bond becomes large, the number of CMP defects once decreases,and, as the proportion of Si—CH2 bond further becomes large, the numberof CMP defects increases again. This is because, as shown in FIG. 4before, when the proportion of Si—CH2 bond becomes large, the proportionof Si—CH3 bond which deteriorates adhesion decreases, and adhesionbetween CAP-SiO2 film and SiOCH film is improved, so that delaminationof CAP-SiO2 film caused by CMP process decreases and defects of Cudecreases. When the proportion of Si—CH2 bond further increases, —CH2-bond is introduced into —O—Si—O— bond, so that the film strengthdeteriorates and the number of defects again increases. Therefore, inorder to keep the number of defects small, it is preferable that theSi—CH2 bond/Si—CH3 bond ratio of the SiOCH film is in a range from 0.03to 0.05. When the Si—CH2 bond/Si—CH3 bond ratio is in this range, it isalso possible to suppress disadvantages such as the delamination ofCAP-SiO2 film when fabricating the device and the like can be avoided.

Embodiment 3

An explanation will now be made on a third embodiment of the presentinvention. In the third embodiment, a dual damascene wiring structure isformed by using an interlayer insulating film according to the presentinvention.

FIGS. 9A–9D are cross sectional views each illustrating, in order ofprocess steps, a workpiece of a semiconductor device according to thethird embodiment of the present invention obtained during a process ofmanufacturing thereof.

With reference to FIG. 9A, first, on a ground insulating film 81 formedon a semiconductor substrate (not shown in the drawing) on whichsemiconductor elements such as transistors, capacitors and the like (notshown in the drawing) are formed, a first interlayer insulating filmcomprising three layers designated by reference numerals 82, 83 and 84are formed in this order from a lower layer to an upper layer, by usingprocess steps similar to those mentioned above with respect to thesecond embodiment. That is, as an anti metal diffusion insulating filmfor preventing diffusion of metal, a first SiCNH film 82 is formed to afilm thickness of 50 nm. Then, a first SiOCH film 83 is formed to a filmthickness of 250 nm. Thereafter, the first SiO2 film (i.e., firstCAP-SiO2 film) 84 is formed to a film thickness of 100 nm.

Next, within a wiring trench formed such that the wiring trenchpenetrates through the first interlayer insulating film, a first Cuwiring conductor 87 which is a first metal wiring conductor is formedvia a first barrier metal Ta/TaN film 86.

With reference to FIG. 9B, a second interlayer insulating filmcomprising three layers 88, 89 and 90 is formed on the SiO2 film 84 andthe upper surface of the first Cu wiring conductor 87. That is, a secondSiCNH film 88 as an anti metal diffusion insulating film is formed to afilm thickness of 50 nm. Then, by using a plasma enhanced CVD method, asecond SiOCH film 89 is formed to a film thickness of 500 nm which hasSi—CH2 bond therein and Si—CH2 bond/Si—CH3 bond ratio thereof ispreferably 0.03–0.05. Thereafter, a second SiO2 film (a second CAP-SiO2film) 90 is formed to a film thickness of 100 nm.

By using a photolithography technology and a dry etching technology,there is formed an opening 91 from the surface of the second SiO2 film90 until it reaches the second SiCNH film 88, as clearly shown in FIG.9B.

Next, with reference to FIG. 9C, by using a photolithography technologyand a dry etching technology, there is formed a wiring trench 94 in anarea including the opening 91. Also, a portion of the SiCNH film 88 atthe bottom portion of the opening 91 is opened, such that the opening 91reaches the upper surface of the first Cu wiring conductor 87 whichbecomes a lower layer metal wiring conductor. In this case, the wiringtrench 94 is formed halfway through the thickness of the second SiOCHfilm 89.

Next, on an inside wall of the opening 91 and the wiring trench 94 andon the upper surface of the second SiO2 film 90, a second Ta/TaN film100 is formed as a barrier metal layer to a film thickness of 30 nm. Onthe second Ta/TaN film 100, a Cu layer is formed to a film thickness of100 nm by using a sputtering method. The Cu layer is used as a Cucontaining metal which becomes a cathode side ground layer for anelectrolytic plating method. Thereafter, the opening 91 and the wiringtrench are filled with Cu as the Cu containing metal by using anelectrolytic plating method. Further, a heat treatment is performed at atemperature of 100–400° C. for crystallization. Then, the Cu layer andthe Ta/TaN film on the second SiO2 insulating film 90 are removed by aCMP method. Thereby, Cu plug and second Cu wiring conductor (designatedby a common reference numeral 101) are simultaneously formed as metalplug and second metal wiring conductor. In this way, a two layer wiringconductor formed by Cu and having a dual damascene structure is formed,as clearly shown in FIG. 9D.

FIG. 10 shows a relationship between the yield from 1,000,000 via chainsof two layer Cu wiring conductors and the Si—CH2/Si—CH3 ratio of anSiOCH film which is used as an interlayer insulating film, when the Cutwo layer wiring conductors are formed in accordance with theabove-mentioned dual damascene method. From FIG. 10, it can be seenthat, as the Si—CH2 bond/Si—CH3 bond ratio becomes small, the yieldbecomes small. This is because, in such case, ashing tolerancedeteriorates, and, therefore, outgassing of moisture and the like fromthe side surface of via forming portion increases, so that via is notcompletely filled with Cu and the like. On the other hand, when theSi—CH2 bond/Si—CH3 bond ratio is too high, the yield becomes small. Itis considered that when the Si—CH2 bond/Si—CH3 bond ratio is too high,the film strength deteriorates so that the interlayer insulating film isdamaged when CMP process is performed. Therefore, in order to obtainhigh yield, it is preferable that the Si—CH2 bond/Si—CH3 bond ratio ofthe SiOCH film is in a range from 0.03 to 0.05.

In the above description, an explanation was made on a method of forminga dual damascene wiring structure, by using a via-first technology inwhich a wiring trench is formed after forming an opening (i.e., a via).However, the present invention is not limited to such method. Forexample, the present invention can also be applied to a trench-firstmethod in which an opening (i.e., a via) is formed after forming awiring trench. It is also possible to use a middle-first method in whichan SiCH film or an SiCNH film which functions as an etching stopperlayer is inserted into the second SiOCH film, and, after processing theetching stopper layer first, a wiring trench and a via opening aresimultaneously formed.

Further, in the second and third embodiments mentioned above, the Cucontaining metal which constitutes the metal wiring conductor (metalwire) and the metal plug was Cu, that is, the metal wiring conductor wasa Cu wiring conductor and the metal plug was a Cu plug. However, the Cucontaining metal can be a Cu containing metal which contains, inaddition to Cu, at least one of: Si, Al, Ag, W, Mg, Be, Zn, Pd, Cd, Au,Hg, Pt, Zr, Ti, Sn, Ni and Fe. In case the Cu containing metal containsthese materials, it is possible to further improve the life of wiringconductors in a semiconductor device which has the structure accordingto the present invention.

According to the above-mentioned constitution of the present invention,an insulating film is provided which is a carbon containing oxidesilicon (SiOCH) film and which has —Si—CH2- bond in the film. Therefore,it becomes possible to improve ashing tolerance, without causing a risein the dielectric constant of the interlayer insulating film whichespecially requires low dielectric constant. Also, as described beforewith reference to FIG. 4, it is possible to improve adhesion to theCAP-SiO2 film.

In the foregoing specification, the invention has been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the present invention as set forthin the claims below. Accordingly, the specification and figures are tobe regarded in an illustrative sense rather than a restrictive sense,and all such modifications are to be included within the scope of thepresent invention. Therefore, it is intended that this inventionencompasses all of the variations and modifications as falling withinthe scope of the appended claims.

1. An insulating film comprising; a carbon containing silicon oxide(SiOCH) film which has Si—CH2 bond in the carbon containing siliconoxide film; wherein the proportion of Si—CH2 bond (1360 cm−1) to Si—CH3bond (1270 cm−1) in the insulating film is in a range from 0.03 to 0.05measured as a peak height ratio of FTIR spectrum.
 2. An insulating filmas set forth in claim 1, wherein the relative dielectric constant of theinsulating film is equal to or lower than 3.1.
 3. An insulating film asset forth in claim 1, wherein the carbon containing silicon oxide(SiOCH) film is formed by using plasma enhanced CVD process.
 4. Aninsulating film as set forth in claim 1, wherein the carbon containingsilicon oxide (SiOCH) film comprises methylsilsesquioxane.
 5. Asemiconductor device having an interlayer insulating film formed on orover a semiconductor substrate and a metal wiring conductor which isformed by filling a wiring trench formed in the interlayer insulatingfilm with Cu containing metal via a barrier metal, wherein theinterlayer insulating film includes the insulating film comprising: acarbon containing silicon oxide (SiOCH) film which has Si—CH2 bond inthe carbon containing silicon oxide film, wherein the proportion ofSi—CH2 bond (1360 cm−1) to Si—CH3 bond (1270 cm−1) in the insulatingfilm is in a range from 0.03 to 0.05 measured as a peak height ratio ofFTIR spectrum.
 6. A semiconductor device as set forth in claim 5,wherein the relative dielectric constant of the insulating film is equalto or lower than 3.1.
 7. A semiconductor device as set forth in claim 5,wherein the carbon containing silicon oxide (SiOCH) film is formed byusing plasma enhanced CVD process.
 8. A semiconductor device as setforth in claim 5, wherein the carbon containing silicon oxide (SiOCH)film comprises methylsilsesquioxane.
 9. A semiconductor device as setforth in claim 5, wherein, as a portion of the interlayer insulatingfilm, an SiO2 film is formed on the upper layer portion of theinsulating film.
 10. A semiconductor device as set forth in claim 5,wherein, as a portion of the interlayer insulating film, an insulatingfilm for preventing metal diffusion is formed on the lower layer portionof the insulating film.
 11. A semiconductor device as set forth in claim5, wherein the Cu containing metal contains, in addition to Cu, at leastone of Si, Al, Ag, W, Mg, Be, Zn, Pd, Cd, Au, Hg, Pt, Zr, Ti, Sn, Ni andFe.